Comprehensive Coordination Chemistry II - From Biology to Nanotechnology 2 ed. in 10 Vol.Set Volume 09 - Applications of Coordination Chemistry

McCleverty J.A. (ed.) Comprehensive Coordination Chemistry II - From Biology to Nanotechnology 2 ed. in 10 Vol.Set Volume 09 - Applications of Coordination Chemistry 2003 [pdf 1062sc 1063+1c. 10.85mb]Comprehensive Coordination Chemistry II (CCC II) is the sequel to what has become a classic in the field, Comprehensive Coordination Chemistry, published in 1987. CCC II builds on the first and surveys new developments authoritatively in over 200 newly comissioned chapters, with an emphasis on current trends in biology, materials science and other areas of contemporary scientific interest. Cover Page 1 Introduction to Volume 9 2 COMPREHENSIVE COORDINATION CHEMISTRY II 4 Volumes 5 Info on Volume 9 6 Volume 9 8 9.1 Metal Complexes as Catalysts for Polymerization Reactions 8 Introduction 9 Olefin Polymerization 9 Introduction 9 Catalyst Survey 10 Group 4 metallocene catalysts 10 Ethylene polymerization 10 Isospecific propylene polymerization 10 Syndiospecific propylene polymerization 12 Elastomeric poly(propylene) 12 Group 4 non-metallocenes 13 Constrained geometry catalysts 13 Nitrogen-based ligands 14 Oxygen based ligands 17 Group 3 and rare earth metal catalysts 18 Group 5 metal catalysts 19 Group 6 metal catalysts 20 Cyclopentadienyl systems 20 Nitrogen- and oxygen-based ligands 20 Group 8 metal catalysts 21 Group 9 metal catalysts 22 Group 10 metal catalysts 22 Main group metal catalysts 24 polymerization of Styrenes 25 Introduction 25 Coordinative Polymerization of Styrenes 25 Atom Transfer Radical Polymerization of Styrenes 27 Polymerization of Acrylates 30 Introduction 30 Anionic Initiators of the group 1, 2, and 3 Metals 30 Well-defined Magnesium and Aluminum Initiators 31 Lanthanide Initiators 33 Early Transition Metal Initiators 34 Atom Transfer Radical Polymerization 36 Ring-Opening Metathesis Polymerization of Cyclic Alkenes 36 Introduction 36 Titanacyclobutanes 36 Group 6 Metal Initiators 37 Ruthenium Initiators 40 Acyclic Diene Metathesis 43 Ring-Opening Polymerization of Cyclic Esters 43 Introduction 43 General Features of Lactone Polymerization 44 Aluminum-based Initiators 44 Zinc-Aluminum Oxo-alkoxide Initiators 49 Magnesium and Zinc Initiators 49 Calcium Initiators 50 Tin Initiators 51 iron Initiators 52 Yttrium and Rare-earth Initiators 53 Titanium and Zirconium Initiators 58 Ring-Opening Polymerization Of Epoxides 59 Introduction 59 Tetraphenylporphyrin Aluminum and Zinc Initiators 59 Non-porphyrinato Aluminum Initiators 61 Copolymerization of Epoxides and Aziridines with Carbon Monoxide 61 Copolymerization of Epoxides and Aziridines with Carbon Monoxide 64 Other Living Coordination Polymerizations 65 ROP of N-carboxyanhydrides and beta-lactams 65 Polymerization of Isocyanates and Guanidines 65 References 66 9.2 Metal Complexes as Hydrogenation Catalysts 82 Introduction 82 Historical Background 83 Homogeneous Hydrogenation 83 Metal Monohydride Mechanism 84 Metal Dihydride Mechanism 87 Asymmetric Hydrogenation Mechanisms 89 Homogeneous Transfer Hydrogenation 99 Direct Hydrogen Transfer Mechanism 100 Metal Monohydride Mechanism 100 Metal Dihydride Mechanism 102 Metal-Ligand Bifunctional Concerted Mechanism 102 Mechanism of Aerobic Alcohol Oxidation 103 Homogeneous Hydrogenolysis 105 Hydrodesulfurization 106 Hydrodenitrogenation 112 New Developments in Hydrogenation 117 Hydrogenation in Aqueous Systems 117 Water-soluble hydrogenation catalysts 118 Immobilization on solids 121 Immobilization via biphasic catalysis 124 Microheterogenization on organized amphiphiles in the colloidal or nanoscale dimension 125 Enantioselective hydrogenation in aqueous systems 127 Transfer hydrogenation and hydrogenolysis in aqueous systems 128 Hydrogenations with CO/H2O mixtures 128 Hydrogenation in Supercritical Carbon Dioxide 129 Hydrogenation by Cluster Catalysis 132 Hydrogenation In Biological Systems 136 References 140 9.3 Metal Complexes as Catalysts for Addition of Carbon Monoxide 147 Introduction 148 Carbonylation of Methanol 148 Rhodium Catalysts 148 Immobilization studies (see also Chapter 9.9) 152 Iridium Catalysts 153 Palladium and Nickel Catalysts 153 Cobalt Catalysts 154 Miscellaneous 154 Reductive carbonylation 154 Calculations 155 Hydroformylation 155 Platinum 155 Cis-PtCl2(PPh3)2SnCl2 systems 155 Studies on the mechanism of catalytic hydroformylation 155 The role of the trichlorostannyl ligand in the Pt-catalyzed hydroformylation 157 Cis-PtCl2(diphosphine)/SnCl2 systems 157 Miscellaneous 158 Palladium 159 Cobalt 160 Rhodium 161 Introduction to phosphine catalysts 161 Introduction to phosphite catalysts 164 Asymmetric Catalysis Using Platinum 172 Chiral diphosphine ligands 172 Aminophosphine-phosphinite ligands 175 Diphosphite ligands 175 Miscellaneous 176 Asymmetric Catalysis Using Rhodium 177 Diphosphines as chiral ligands 177 Diphosphite ligands 178 Phosphine-phosphite ligands 180 Miscellaneous 182 Two-phase catalysis 182 Palladium-Catalyzed Alternating Copolymerization of Alkenes And Carbon Monoxide 185 Reductive Carbonylation Of Nitro Compounds 190 Introduction 190 Ruthenium catalysts 191 Palladium catalysts 191 Rhodium catalysts 192 Amidocarbonylation 192 Palladium catalysts 193 Cobalt catalysts 193 Hydroxycarbonylation 194 Palladium/Phosphorus Complexes in Hydroxycarbonylation 195 Palladium Species Involved in the Hydroxycarbonylation Reaction 196 Methoxycarbonylation 197 Mechanistic studies 198 Palladium complexes involved in the methoxycarbonylation reaction 199 Phosphorus ligands in Pd methoxycarbonylation 199 Asymmetric methoxycarbonylation 200 References 200 9.4 Metal Complexes as Catalysts for Oxygen, Nitrogen, and Carbon-atom Transfer Reactions 213 Introduction 213 Epoxidation 214 Epoxidation of Allylic Alcohols 214 Epoxidation of Isolated Olefins 217 Epoxidation using metalloporphyrin as catalysts 217 Epoxidation using metallosalen complexes as catalysts 222 Epoxidation of Electron-deficient Olefins 229 Oxidation of Enol Ethers and their Derivatives 231 Asymmetric Aziridination 233 Asymmetric Dihydroxylation 237 General Features of Asymmetric Dihydroxylation 237 Mechanistic Considerations 241 Models for the Enantiodifferentiating Step in Dihydroxylation 244 Iron-mediated Dihydroxylation 244 Asymmetric Aminohydroxylation 245 Asymmetric Cyclopropanation 249 Asymmetric Intermolecular Cyclopropanation 249 Cu-catalyzed cyclopropanation 249 Rh-catalyzed cyclopropanation 251 Ru-catalyzed cyclopropanation 254 Co-catalyzed cyclopropanation 256 Asymmetric Intramolecular Cyclopropanation 257 Cu-catalyzed cyclopropanation 257 Rh-catalyzed cyclopropanation 258 Ru-catalyzed cyclopropanation 259 Co-catalyzed cyclopropanation 260 Mechanism of Cyclopropanation 261 Conclusion 264 References 265 9.5 Metal Complexes as Catalysts for H-X (X=B, CN, Si, N, P) Addition to CC Multiple Bonds 271 Introduction 271 Hydroboration 272 Developments Since CCC (1987) 272 Ligand Effects in Rhodium-catalyzed Hydroboration of Vinylarenes 275 Metal-catalyzed Hydroboration of Other C=C Bonds 276 Hydroboration of Substrates Containing C=C Bonds: Enynes and Alkynes 276 Asymmetric Hydroboration 277 Hydrocyanation 281 Reactions of Nonactivated Alkenes 282 Hydrocyanation of Activated Alkenes 283 Hydrosilylation 286 Developments in Achiral Catalytic Si-H Addition 286 Asymmetric Hydrosilylation 287 Enantioselective Hydrosilylation Employing Chiral Ferrocenyl Phosphine Ligands 291 Intramolecular Asymmetric Hydrosilylation 292 Enantioselective Hydrosilylation of C=O and C=N Bonds-A Brief Synopsis 294 Hydroamination 294 Mechanism and Early Transition Metal/Lanthanide Catalysts 294 Rhodium and Iridium Catalysts 297 Palladium and Platinum Catalysts 300 Hydrophosphination (And Hydrophosphorylation) 302 Hydrophosphination 303 Hydrophosphorylation and Hydrophosphinylation 304 References 307 9.6 Metal Complexes as Catalysts for C-C Cross-coupling Reactions 311 Introduction 312 Notation used in examples 313 Major Methods of Cross-Coupling 313 Cross-coupling with Organoboron Compounds 314 Cross-coupling with Organotin Compounds 316 Cross-coupling with Organozinc Reagents 318 Cross-coupling with Organomagnesium and Organolithium Reagents 321 Cross-coupling with Terminal Acetylenes 322 The Development of the Cross-Coupling Methodology 324 Less Common Nucleophilic Reagents 325 Less common organometallics 325 Copper 325 Mercury 325 Aluminum 326 Gallium 326 Indium 326 Germanium 327 Titanium 327 Zirconium 327 Bismuth 328 Manganese 328 Electrochemical cross-coupling 328 CH-nucleophiles 328 Activation of Cross-coupling Reactions 331 Electrophilic catalysis 331 Copper 331 Activation of the nucleophilic reagent 333 Various activation methods in the cross-coupling of organosilicon compounds 337 Compounds with Si-O bonds 337 Tetraorganosilanes 339 Nonfluoride activation 340 Leaving Groups 340 Fluorides 341 Chlorides 341 Esters as electrophiles in cross-coupling reactions 342 Other neutral electrophiles 344 Sulfur derivatives 344 Se and Te derivatives 346 Organometallic compounds of main group metals 347 Diazonium salts 347 Iodonium salts 347 Catalysts 347 Monophosphine catalysis 349 Chelating ligands with both phosphine and nonphosphine binding sites 349 Bulky trialkyl- and dialkylphosphines 351 Bulky dialkylarylphosphines 353 Heterobimetallic complexes 353 Phosphorus ligands other than phosphines 354 Bidentate diphosphine ligands 355 Palladacycles 357 PC-Palladacycles 357 NC and OC-palladacycles 357 Nonphosphorus ligands 358 Heterocyclic carbene ligands 359 Palladium nanoparticles and "ligand-free" catalysis 362 Technological Aspects of Cross-coupling Chemistry 362 Microwave heating 363 Supported catalysts 363 Physical absorption on inorganic or similar supports 363 Pd/C and Ni/C 363 Polymer-immobilized catalysts 364 Aqueous systems 365 Fluorous systems 365 Supercritical CO2 365 Ionic liquids 366 References 366 9.7 Metal Complexes as Catalysts for Carbon-heteroatom Cross-coupling Reactions 375 Introduction 375 Early Examples 377 Scope of the Reactions 378 Initial Intermolecular Tin-free Aminations of Aryl Halides 378 Second Generation Catalysts Bearing Aromatic Bisphosphines 378 Amination of aryl halides 378 Amination of aryl triflates 379 Amination of heteroaromatic halides 380 Third-generation Catalysts Bearing Alkylmonophosphines 380 Sterically hindered bisphosphine ligands for aminations 381 P,N, P,O, and dialkylphosphinobiaryl ligands 382 Low-temperature reactions catalyzed by P(t-Bu)3 complexes 383 Heterocyclic carbenes as ligands 383 Phosphine oxide ligands 384 Heterogeneous Catalysts 384 Aromatic C-N Bond Formation with Related Substrates 384 Etherification 387 Initial Studies with Arylphosphines 388 Second-generation Catalysts Containing Sterically Hindered Alkylphosphines 388 Carbon-Sulfur and Carbon-Selenium Bond-Forming Cross-Couplings 390 Carbon-Phosphorus Bond-Forming Cross-Couplings 392 Coupling of Aryl and Vinyl Halides with Phosphorus(V) Reagents 392 Coupling of Aryl and Vinyl Halides with Phosphorus(V) Reagents 393 Coupling of Aryl Halides with Silanes, Stannanes, Germanes, and Boranes 394 Coupling with Silanes, Stannanes, and Germanes 394 Coupling with Boranes 395 Intermediates in the Coupling Chemistry 396 References 400 9.8 Metal Complexes as Lewis-acid Catalysts in Organic Synthesis 405 Introduction 405 Alkali Metals 405 Magnesium 407 Scandium and Lanthanides 408 Titanium 411 Zirconium 421 Hafnium 422 Copper 425 Silver and Gold 427 Zinc 428 Other Transition-Metal Lewis Acids 430 Boron 432 Aluminum 435 Silicon 436 Tin 439 Others 441 Conclusion/Classification of Lewis Acids 443 References 445 9.9 Supported Metal Complexes as Catalysts 451 Introduction 451 The Different Procedures of Immobilization of Metal Complexes on Solid Supports 452 Introduction 452 Direct Reaction between the Solid Support and the Metal Complex 452 Inorganic supports 452 Incorporation by ion exchange reactions 452 Incorporation by covalent anchoring 455 Organic supports 456 Incorporation by ion exchange reactions 456 Incorporating by covalent bonding 457 Immobilization by Copolymerization 458 Inorganic matrices 458 Organic supports 459 Supported Liquid Phase Catalysts (SLPC) 460 Some Reactions Catalyzed By Supported Metal Complexes 462 Hydrogenation 462 Epoxidation 464 Supported titanium-based catalysts 464 Supported salen-type complexes 467 C-C Bond Formation by Cross Coupling 469 Heck reaction 469 Trost-Tsuji allylic substitution 471 Polymerization 472 Conclusion And Perspectives 473 References 473 9.10 Electrochemical Reactions Catalyzed by Transition Metal Complexes 477 Introduction 478 Basic Principles 478 Electrocatalytic Reduction Of Protons And Hydride Transfer Reactions 479 Metal Hydride Complexes: Electrogeneration and Electrocatalytic Dihydrogen Evolution 479 Transition metal macrocycles 480 Polypyridyl complexes 481 Phosphine complexes 482 Miscellaneous complexes 482 Electrochemically Driven Hydride Transfer Reactions 483 Electrocatalytic regeneration of reduced nicotinamide cofactors 483 Electrocatalytic hydrogenation of organics 483 Electrocatalytic Reduction Of Carbon Dioxide 484 Polypyridyl Metal Complexes 485 Re(bpy)(CO)3Cl and related complexes 485 [Ru(bpy)2(CO)2]2+ and related complexes 486 Other polypyridyl metal complexes 487 Metal Complexes with Macrocycles 488 Phthalocyanine complexes 488 Porphyrin complexes 488 Cyclam and other polyazamacrocyclic complexes 489 Phosphine Complexes and Miscellaneous Complexes 490 Phosphine complexes 490 Other complexes 490 Carboxylation of Organic Substrates 490 Electrocatalytic Reduction Of Organic Halides 491 Polypyridyl Complexes 491 Reductive homo- and heterocoupling of organic halides 491 Carbonylation of organic halides 492 Phosphine Complexes 492 Electroreductive coupling of organic halides 492 Carbonylation and carboxylation of organic halides 493 Schiff Bases and Macrocyclic Nickel and Cobalt Complexes 493 NiII and CoI Schiff base complexes 493 NiII complexes of cyclams and other tetradentate N-ligands 494 Vitamin B12 derivatives and model complexes 495 Electrocatalytic Reduction of Dinitrogen and Nitrogen Oxides 496 Electrocatalytic Activation of Dinitrogen 496 Electrocatalytic Conversion of Nitrate to Ammonia 496 Electrocatalytic Reduction of Nitrite and Nitric Oxide 497 Metal complexes of nitrogen macrocycles 497 Polypyridyl complexes 498 Polyaminocarboxylate complexes 498 Electrochemical Sensors for Nitrite and Nitric Oxide Determination 498 Electrocatalytic Reduction and Activation of Dioxygen 499 Electrocatalytic Four-electron Reduction of Dioxygen 499 Electrocatalytic P-450 Model Systems 501 The Gif-Orsay System 502 Electrocatalytic Oxidation of Water and Organics 503 Oxidation of Water 503 Oxidation of Organics 504 References 506 9.11 Combinatorial Methods in Catalysis by Metal Complexes 514 Introduction 514 Achiral Catalytic Processes 515 Hydrolysis Reactions 515 Hydrosilylation of Olefins and Imines 517 Heck Reactions 517 Hydroamination Reactions 519 Allylic Substitution 519 Annulation Reactions 521 Epoxidation Reactions 521 Ring-closing Olefin Metathesis 521 Reductive Aldol Addition 523 Olefin Polymerization 523 Novel Strategies in the Design of Ligand Libraries 527 Enantioselective Processes 528 High-throughput ee-Assays 529 Strategies Used in the Combinatorial Design and Preparation of Enantioselective Transition Metal Catalysts 540 Conclusions and Perspectives 550 References 551 9.12 Metal Complexes as Speciality Dyes and Pigments 554 Introduction 554 Nature of Bonding In Metal Complex Azo Colorants 556 Azo/Hydrazone Tautomerism 557 Nature of Azo-to-metal Bonding 558 Effect Of Metallization on Properties 560 Lightfastness 560 Color 561 Textile And Related Applications 562 Azo Dyes 562 Azo Pigments 564 Phthalocyanine Dyes and Pigments 565 Formazan Dyes 566 Ortho-hydroxy Nitroso Dyes and Pigments 568 Others 568 Electrophotography (Laser Printing And Photocopying) 568 Laser Printing Process 568 Organic Photoconductors 569 Toners 571 Ink Jet Printing 572 Ink Jet Printing Process 573 Ink Jet Dyes and Pigments 574 Infrared Absorbers 577 Silver Halide Photography 579 Miscellaneous Applications 579 Dark Oxidation Catalysts 579 Singlet Oxygen Generators 580 Organic Semiconductors 581 Toxicological And Ecotoxicological Considerations 581 References 582 9.13 Metal Complexes as Dyes for Optical Data Storage and Electrochromic Materials 585 Electrochromic Dyes 585 Introduction 585 Classes of Electrochromic Material 586 Electrochromism in Transition Metal Coordination Complexes 587 Electrochromism of polypyridyl complexes 587 Polypyridyl complexes in solution 587 Reductive electropolymerization of polypyridyl complexes 588 Oxidative electropolymerization of polypyridyl complexes 588 Spatial electrochromism of polymeric polypyridyl complexes 589 Electrochromism in metal phthalocyanines and porphyrins 590 Introduction to metal phthalocycanines and porphyrins 590 Sublimed bis(phthalocyaninato) lutetium(III) films 590 Other metal phthalocyanines 592 Electrochemical routes to metallophthalocyanine electrochromic films 592 Langmuir-Blodgett metallophthalocyanine electrochromic films 593 Species related to metal phthalocyanines 594 Electrochromic properties of porphyrins 594 Prussian blue systems 595 Prussian blue systems: history and bulk properties 595 Preparation of Prussian blue thin films 595 Electrochemistry, in situ spectroscopy, and characterization of Prussian blue thin films 596 Prussian blue electrochromic devices 598 Prussian blue analogs 599 Near-infrared region electrochromic systems 601 Significance of the near-infrared region 601 Planar dithiolene complexes of Ni, Pd, and Pt 601 Mixed-valence dinuclear complexes of ruthenium 602 Tris(pyrazolyl)borato-molybdenum complexes 602 Ruthenium and osmium dioxolene complexes 605 Metal Complexes as Dyes for Optical Data Storage 606 Background 606 Optical Data Storage Categories 606 Read only media 606 Write-once recordable media: CD-R and DVD-R 609 Rewriteable media 611 Optical Data Storage on Write-once Media 611 Heat-mode recording 611 CD-R: Recording mechanism 612 Brief history of development of dyes for optical data storage 612 Specific requirements for dyes for optical disk recording 613 Phthalocyanines and related compounds 614 Metal complexes of azo dyes 618 Future Developments 619 References 619 9.14 Nonlinear Optical Properties of Metal Complexes 624 Introduction 624 General Context and Scope of this Review 624 The Origins of NLO Behavior in Molecular Materials 625 Requirements for NLO Activity 626 Measurement of NLO Properties 626 Why are Metal Complexes of Interest? 629 Coordination Complexes with Nlo Properties 630 Complexes of Nonchelating Pyridyl Ligands 630 Complexes of Chelating Pyridyl Ligands 635 Complexes of Porphyrin and Related Ligands 641 Complexes of Phthalocyanine and Naphthalocyanine Ligands 646 Complexes of Schiff Base Ligands 653 Complexes of Thiocyanate Ligands 658 Complexes of 1,2-Dithiolene and Related Ligands 659 Cluster Complexes 662 Miscellaneous Complexes 670 Conclusions 676 References 678 9.15 Metal Compounds as Phosphors 691 Introduction 692 History of Phosphors and Past Uses 692 Current Uses Of Phosphors 693 Display Technologies Using Phosphors 693 Cathode Ray Tube Displays 693 Electroluminescent Displays 694 Vacuum Fluorescent Displays 698 Field Emission Displays 698 Plasma Displays 699 Phosphor Synthesis 699 Traditional Solid-state Synthesis 700 Hydrothermal and Related Methods 700 Homogeneous precipitation 700 Sol-gel methods 703 Microemulsion methods 703 Other Solution-based Techniques 704 Combinatorial methods 704 Solution-coating methods 704 Vapor-phase Methods 704 Chemical vapor deposition 704 Molecular beam epitaxy and its derivatives 704 RF magnetron sputtering 705 Electron beam evaporation 705 Pulsed laser decomposition 705 Ion implantation 705 Aerosol spray pyrolysis 706 Charged liquid cluster beam methods 706 Organo-Electroluminescent Devices 706 Coordination Compounds as Organo-electroluminescent Devices 706 Group II metal complexes 706 Tris(8-hydroxyquinolato)aluminum and related complexes 707 Lanthanide beta-diketonate complexes 709 Other metal complexes 710 Novel Organo-electroluminescent Devices/Inorganic Devices 711 Problems with Organo-electroluminescent Devices 711 Light-Emitting Diodes 711 Anti-Stokes Phosphors 711 Quantum Cutters 712 Novel Inorganic-Based Luminous Materials 713 Phosphorescent Paints 713 Photonics 713 The Future 714 References 714 9.16 Conversion and Storage of Solar Energy using Dye-sensitized Nanocrystalline TiO2 Cells 720 Concepts and Definitions 721 Overview 721 Dye-sensitized Solar Cell 722 Dye-sensitized Solar Cell Fabrication 722 Operating Principles of the Dye-sensitized Solar Cell 722 Incident Photon-to-current Efficiency 724 Open-circuit Photovoltage 724 Fill Factor 724 Power Conversion Efficiency 725 Solar Radiation and Air Mass 725 Photophysical Properties of Metal Complexes 725 Semiconductor Films 726 Preparation of Mesoscopic TiO2 Colloids 726 Preparation of Films 727 Molecular Sensitizers 728 Requirements of the Sensitizers 728 Tuning of MLCT Transitions 729 Spectral Tuning in "Push-Pull" Type Complexes 729 Osmium Complexes 734 MLCT Transitions in Geometrical Isomers 734 Sensitizers Containing Functionalized Hybrid Tetradentate Ligands 734 Hydrophobic Sensitizers 736 Near IR Sensitizers 738 Ruthenium phthalocyanines 739 Phthalocyanines containing 3d metals 739 Surface Chelation and Electron Injection 741 Surface Chelation 741 X-ray Diffraction, X-ray Photoelectron Spectroscopy, and XAFS Spectroscopy Study 742 Acid-base Equilibria of cis-Dithiocyanato-bis(2,2'-bipyridine-4,4'-dicarboxylate) Ruthenium(II) 743 ATR-FTIR Studies of Sensitizer Adsorption on TiO2 Oxide Surface 743 Effect of Protons Carried by the Sensitizer on the Performance 744 Comparison of IPCE Values Obtained with Various Sensitizers 745 Electron Injection Kinetics 747 Redox Mediators 748 New Redox Couples 748 Solid Electrolytes/Hole-transport Materials 749 Energy Conversion and Storage 750 Water Splitting by Visible Light using a Tandem cell 750 Synthesis and Characterization of Complexes 751 Synthetic Strategies for Ruthenium Complexes 751 Purification 753 Characterization 753 Conclusions and Perspectives 756 Acknowledgements 756 References 757 9.17 Metal Complexes for Hydrometallurgy and Extraction 760 Introduction 760 Mineral Processing 763 Leaching 764 Leaching of Gold and Silver into Basic Media 765 Leaching of Gold and Silver into Acidic Media 766 Leaching of Base Metals 767 Leaching of base metals into sulfate media 767 Leaching of base metals into chloride media 768 Leaching of base metals into ammoniacal media 769 Separation And Concentration 769 Solvent Extraction Processes 770 Hydroxy-oxime Extractants 771 Organophosphorus Acid Extractants 773 Carboxylic Acids 773 Amine Salt Extractants 775 Solvating Extractants 776 Base Metals 777 Copper 777 Extraction of CuII from sulfate solutions 777 Extraction of CuII from chloride solutions 779 Extraction of CuII from ammoniacal solutions 781 Recovery of CuII from secondary sources 782 Zinc 782 Extraction of ZnII from sulfate media 783 Extraction of ZnII from chloride media 784 Zn/Fe recovery from secondary sources 786 Nickel and Cobalt 786 Co/Ni separation in sulfate solutions 787 Co/Ni separation in chloride and ammoniacal solutions 789 Precious Metals 791 AuI, AuIII 792 AgI 794 PtIV, PtII 795 PdII 797 Conclusions 798 References 798 9.18 Metal Complexes as Drugs and Chemotherapeutic Agents 810 Introduction 810 Biological Assays 811 Platinum Complexes As Therapeutic Agents 813 Clinically Used Anticancer Agents. Cis-platinum Compounds 813 Platinum Compounds in Clinical Trials 818 AMD473 (ZDO-473) 818 JM-216 (Satraplatin) 819 Poly (di and tri)-nuclear platinum complexes 820 BBR3464. A trinuclear platinum clinical agent 820 DNA binding of polynuclear platinum compounds 822 Aquation of dinuclear and trinuclear platinum agents 822 Reactions with oligonucleotides 822 Site-specific intrastrand and interstrand cross-links of BBR3464. Bending, protein recognition and nucleotide excision repair 824 Transplatinum compounds 824 Nonplatinum Anticancer Agents 826 Ruthenium Complexes 826 Arsenic Trioxide 827 The Mitochondrion as Target. Gold-phosphane Complexes 828 Manganese-based Superoxide Dismutase Mimics 828 Titanium Compounds 830 Gallium Nitrate 831 Antibacterial Agents 831 Silver and Mercury Salts 831 Bismuth-containing Antiulcer Drugs 832 Metal-containing Drugs as Antiparasitic Agents 832 Pharmacodynamic Uses of Metal Complex Drugs 833 Lithium Carbonate 833 Vanadium Complexes in Diabetes 834 Gold Compounds as Antiarthritic Agents 834 Nitric Oxide in Physiology and Medicine 835 Lanthanum Carbonate 835 References 835 9.19 Metal Complexes as MRI Contrast Enhancement Agents 842 Introduction 842 Relaxivity of GdIII Complexes 844 Inner-sphere Proton Relaxivity 846 Hydration number and Gd-H distance 848 Water/proton exchange 848 Rotation 852 Electron spin relaxation 852 Outer and Second-sphere Relaxation 854 NMRD Profiles 854 Toxicity of GdIII Complexes: Thermodynamic Stability and Kinetic Intertness 854 Complex Stability Constants 855 Blood Plasma Models 857 Kinetic Inertness of GdIII Complexes 858 Blood Pool Agents 858 Covalently Bound Macromolecular Agents 859 GdIII chelates covalently bound to proteins 859 Linear polymers 859 Dendrimers 860 Dextran derivatives 862 Micelles and liposomes 862 Noncovalently Bound Macromolecular Agents 863 Smart Contrast Agents 867 pH-sensitive Agents 867 Temperature-sensitive Agents 871 Contrast Agents Sensitive to Partial Oxygen Pressure 872 Enzymatically Responsive Contrast Agents 872 Contrast Agents Responsive to Metal Ion Concentration 874 Chemical Exchange Saturation (CEST) Contrast Agents 875 Targeting Contrast Agents 876 References 878 9.20 Radioactive Metals in Imaging and Therapy 883 Introduction 883 Diagnostic Imaging 884 Radiotherapy 885 Nuclear and Physical Properties Needed for Imaging and Therapy 886 Radionuclide Production 887 Cyclotron- or Accelerator-produced Radionuclides 887 Gallium 887 Copper 887 Tin 888 Rubidium 888 Thallium 888 Reactor-produced Radionuclides 888 Strontium 888 Yttrium 888 Radiolanthanides 888 Rhodium 889 Gold 890 Scandium 890 Actinium 890 Lead and Bismuth 890 Pharmaceutical Applications of Radionuclides 891 Gallium, Indium, and Yttrium 891 Copper 894 Radiolanthanides 897 Rhodium 902 Gold 902 Scandium 903 Tin 903 Thallium 903 Rubidium 904 Strontium 904 Actinium 904 Bismuth and Lead 905 Summary 906 Acknowledgement 906 References 906 9.21 Fluorescent Complexes for Biomedical Applications 912 Introduction and Scope 912 Physical Background to Luminescence 913 Organic Molecules as Luminescent Probes for Metal Ions 913 Lanthanide Complexes as Probes: Basic Photophysical Properties 916 Long-lived Luminescence and Time-gating 917 Sensitization of Luminescence: Energy Transfer 918 Triplet-mediated energy transfer 920 Energy transfer mediated by LMCT 921 Solvent Effects on Lanthanide Luminescence 922 Long-wavelength Sensitization and Near-IR Luminescence 923 Lanthanide Complexes in Biological Assays 926 Background 926 The DELFIA Assay 929 The CYBERFLUOR Assay 930 Enzyme-amplified Lanthanide Luminescence (EALL) 933 Homogeneous Assays: DEFRET 933 Assays with Near-IR Luminescent Lanthanides 934 Use of Other Metal Ions in Assays 935 Lanthanide Complexes for Imaging 935 Responsive Lanthanide Complexes as Sensors 938 Conclusions 940 References 940 9.22 Metal Complexes for Photodynamic Therapy 944 Introduction 945 Photodynamic Therapy 946 The Photodynamic Effect and Photodynamic Therapy 946 Mechanistic Aspects 946 Haematoporphyrin Derivative 949 Design Features for a Good Photosensitizer for PDT 949 Photosensitizers in Clinical Use 952 Coordination Complexes as PDT Sensitizers: Some General Considerations 954 Synthesis of Metalloporphyrins and Metallophthalocyanines 954 Metalation of the preformed ligand 954 Transmetalation 955 Template synthesis 955 Metal Complex Stability 955 Structural Variation 958 Solubility 958 Disaggregation 959 Spectroscopic Properties 960 Redox Properties 963 Drug Delivery Systems 965 Complexes of Group 2 966 Magnesium 966 Complexes of Group 3 969 Lanthanides 969 Complexes of Group 7 971 Manganese 971 Technetium 971 Complexes of Group 8 971 Ruthenium 971 Complexes of Group 10 972 Nickel 972 Palladium 974 Platinum 976 Complexes of Group 11 976 Copper 976 Gold 978 Complexes of Group 12 978 Zinc 978 Porphyrin complexes 978 Zinc chlorins and bacteriochlorins 979 Zinc phthalocyanines 980 Zinc naphthalocyanines 983 Other zinc complexes 984 Cadmium 984 Complexes of Group 13 985 Boron 985 Aluminum 986 Gallium 989 Indium 990 Complexes of Group 14 990 Silicon 990 Germanium 991 Tin 992 Conclusions 993 Acknowledgement 994 References 994 9.23 Coordination Complexes as Precursors for Semiconductor Films and Nanoparticles 1003 Introduction 1004 Compound Semiconductors 1004 III-V Materials 1006 II-VI Materials 1006 Thin Films from Vapor-phase Deposition Techniques 1006 Precursor Volatility by Molecular Design 1009 New Delivery Approaches 1009 Related Deposition Techniques 1010 Coordination Chemistry Methods Used for Purification of Metal Alkyl Precursors: "Adduct Purification" 1010 Purification of Group 12 Metal Alkyls 1013 Purification of Group 13 Metal Alkyls 1015 Modified Adduct Purification Techniques 1017 Precursors for Fabrication of II-VI Thin Films 1018 New Group 12 Precursors 1019 New Group 16 Precursors 1019 Precursors for Fabrication of III-V Thin Films 1019 Aluminum Compounds 1020 Gallium Compounds 1021 Indium Compounds 1022 Nitrogen Compounds 1024 Phosphorus Compounds 1025 Antimony Compounds 1025 Arsenic Compounds 1025 Single-Molecule Approach to the Deposition of Compound Semiconducting Materials by Mocvd 1027 Single-molecule Precursors for II-VI Materials 1027 Dialkyldichalcogenocarbamato compounds 1027 Asymmetric dialkyldichalcogenocarbamato precursors 1029 Lewis base adducts of bis(dialkyldithiocarbamato) compounds 1029 Mixed alkyl/dichalcogenocarbamate complexes 1030 Mixed alkyl/dichalcogenocarbamate complexes as precursors for ternary materials 1031 Monothiocarbamate and monothiocarboxylate compounds 1031 Other chalcogenide-based compounds 1032 Chalcogenide-based compounds with high volatility 1032 Thiophosphinates and related compounds 1035 Single-molecule Precursors for III-V Compounds 1035 Dimeric precursor compounds 1037 Monomeric precursor compounds 1037 Trimeric precursor compounds 1038 Nitride Films from Single-molecule Precursors 1038 Gr